EP1578810B1 - Fast moisture curing and uv-moisture dual curing compositions - Google Patents
Fast moisture curing and uv-moisture dual curing compositions Download PDFInfo
- Publication number
- EP1578810B1 EP1578810B1 EP03777610A EP03777610A EP1578810B1 EP 1578810 B1 EP1578810 B1 EP 1578810B1 EP 03777610 A EP03777610 A EP 03777610A EP 03777610 A EP03777610 A EP 03777610A EP 1578810 B1 EP1578810 B1 EP 1578810B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- phenyl
- composition
- curing
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 230000009977 dual effect Effects 0.000 title claims description 4
- 238000013008 moisture curing Methods 0.000 title abstract description 14
- 238000001723 curing Methods 0.000 title description 25
- 238000000034 method Methods 0.000 claims abstract description 11
- -1 siloxane backbones Chemical group 0.000 claims description 42
- 229920000642 polymer Polymers 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 27
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 4
- VWHSLUXEUKWKGT-UHFFFAOYSA-N COc1cccc(OC)c1C(=O)C(C(C)CC(C)(C)C)P(=O)C(C(C)CC(C)(C)C)C(=O)c1c(OC)cccc1OC Chemical compound COc1cccc(OC)c1C(=O)C(C(C)CC(C)(C)C)P(=O)C(C(C)CC(C)(C)C)C(=O)c1c(OC)cccc1OC VWHSLUXEUKWKGT-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 4
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 2
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims description 2
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 claims description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 abstract description 27
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 20
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052710 silicon Inorganic materials 0.000 abstract description 19
- 229920001296 polysiloxane Polymers 0.000 abstract description 17
- 239000010703 silicon Substances 0.000 abstract description 15
- 230000007704 transition Effects 0.000 abstract description 10
- 230000002349 favourable effect Effects 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 238000000016 photochemical curing Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 150000004756 silanes Chemical class 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000001979 organolithium group Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- SMQSEORQRQNSJA-UHFFFAOYSA-N prop-2-enoyloxymethylsilyl 3-methylbut-2-enoate Chemical compound C(C=C)(=O)OC[SiH2]OC(C=C(C)C)=O SMQSEORQRQNSJA-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- KLAMVBJBHNQYSB-UHFFFAOYSA-N 2-ethyl-1-phenylbutan-1-one Chemical compound CCC(CC)C(=O)C1=CC=CC=C1 KLAMVBJBHNQYSB-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- FPOSCXQHGOVVPD-UHFFFAOYSA-N chloromethyl(trimethoxy)silane Chemical compound CO[Si](CCl)(OC)OC FPOSCXQHGOVVPD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- OTAZHVFNECCKIR-UHFFFAOYSA-N C(CCCCCCC)C(CCC)[Li] Chemical compound C(CCCCCCC)C(CCC)[Li] OTAZHVFNECCKIR-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical class CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- ZAZUOXBHFXAWMD-UHFFFAOYSA-N butyl 2-oxopropanoate Chemical class CCCCOC(=O)C(C)=O ZAZUOXBHFXAWMD-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- PBGGNZZGJIKBMJ-UHFFFAOYSA-N di(propan-2-yl)azanide Chemical compound CC(C)[N-]C(C)C PBGGNZZGJIKBMJ-UHFFFAOYSA-N 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical class [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WDDOQHLJFOUQMW-UHFFFAOYSA-N lithium;ethynyl(trimethyl)silane Chemical compound [Li+].C[Si](C)(C)C#[C-] WDDOQHLJFOUQMW-UHFFFAOYSA-N 0.000 description 1
- GNSLYOGEBCFYDE-UHFFFAOYSA-N lithium;ethynylbenzene Chemical compound [Li+].[C-]#CC1=CC=CC=C1 GNSLYOGEBCFYDE-UHFFFAOYSA-N 0.000 description 1
- KBJKWYZQIJZAOZ-UHFFFAOYSA-N lithium;oxidosilane Chemical class [Li+].[SiH3][O-] KBJKWYZQIJZAOZ-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920002631 room-temperature vulcanizate silicone Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- UQMGAWUIVYDWBP-UHFFFAOYSA-N silyl acetate Chemical class CC(=O)O[SiH3] UQMGAWUIVYDWBP-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000759 toxicological effect Toxicity 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- IJQHYEFNLXHUGV-UHFFFAOYSA-N trimethoxysilylmethyl acetate Chemical compound CO[Si](OC)(OC)COC(C)=O IJQHYEFNLXHUGV-UHFFFAOYSA-N 0.000 description 1
- PGOLTJPQCISRTO-UHFFFAOYSA-N vinyllithium Chemical compound [Li]C=C PGOLTJPQCISRTO-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
- C08K5/31—Guanidine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
Definitions
- the invention provides fast moisture and photo/moisture curing silicone compositions and methods for the preparation thereof. More particularly, the compositions provided are prepared from silanol and silane cappers; the cappers have an ⁇ -carbon bonded to the silicon atom allowing for a favorable hypervalent silicon transition state when reacting the silane and silanol. This favorable transition state enables both a fast endcapping reaction and contributes to the fast moisture curing properties of the inventive compositions.
- silanol terminated polydimethylsiloxane can be readily endcapped with acryloxymethyldimethylacryloxysilane by simply mixing this silane with silanol terminated PDMS.
- the reaction is generally complete within seconds after mixing as evidenced by the transformation of the clear silanol fluid into a cloudy mixture due to the low solubility of the liberated acrylic acid in silicone. Removal of acrylic acid by vacuum stripping, if needed, yields the clear acrylate endcapped polydimethylsiloxane.
- Addition of a photoinitiator, fillers and other types of additives common to RTV silicones results in photo (i.e. ultraviolet or "UV") curable silicones.
- photocurable silicon compositions have been developed using cappers such as acryloxymethyldimethylacryloxysilane that allow for a favorable silicon transition state resulting in fast endcapping reactions, compositions derived from such cappers that will result in moisture or dual (UV/moisture) curing silicone compositions are needed.
- compositions capable of fast moisture cure may be exclusively moisture curing or dual (photo/moisture) curing.
- the silanes contain a single carbon linkage between the silicon atom and, for example, an acetyl or methacryloyl group (see structure I below). This linkage provides for the formation of a favorable hypervalent silicon transition state, allowing fast nucleophilic substitution on silicon during endcapping and curing reactions.
- composition including:
- a curable composition having a silane capper compound of the formula: wherein R is a C 1-20 alkyl which may be substituted or unsubstituted or an unsaturated free radical-curing group; R 1 is hydrogen or a C 1-6 hydrocarbon radical; R 2 is a hydrolyzable group; X is oxygen or R 3 is H or C 1-12 hydrocarbyl group; and a silanol-terminated polymer having the structure: wherein A is a backbone selected from the group consisting of organic and siloxane backbones, and R e is CH 3 or H.
- R 2 is selected from the group consisting of (R) 2 ""N and R 4 O wherein R', R", R"' and R"" is H or a monovalent substituted or unsubstituted C 1-6 hydrocarbon radical, and R 4 is a C 1-2 alkyl group.
- R 2 is selected from the group consisting of (CH 3 ) 2 N- and R 4 O wherein R 4 is a C 1-2 alkyl group.
- R 2 is an alkoxy group having the formula R 4 O- wherein R 4 is a C 1-2 alkyl group.
- R is a C 1-20 alkyl or C 2-20 alkenyl either of which may be substituted or unsubstituted.
- both moisture and photo curable groups are present on the silane capper of the invention.
- the composition includes a silane capper wherein R includes an unsaturated free radical-curing group (i.e. a C 2-20 alkenyl which may be substituted or unsubstituted), capable of undergoing free radical cure, such as UV cure, and R 1 , R 2 , X, and R 3 are as described above and structural formula II is as described above.
- R includes an unsaturated free radical-curing group (i.e. a C 2-20 alkenyl which may be substituted or unsubstituted), capable of undergoing free radical cure, such as UV cure
- R 1 , R 2 , X, and R 3 are as described above and structural formula II is as described above.
- a moisture curable composition wherein the silane capper exclusively includes moisture curable groups.
- the composition includes structural formula I wherein R is a C 1-20 alkyl which may be substituted or unsubstituted, R 1 , R 2 , X, and R 3 are as described above, and structural formula II is as described above.
- the most desirable silane capper has the general formula III wherein R, R 1 , R 2 and R 4 are as described above.
- a preferred class of such compounds includes those in which the alkoxyfunctional silane contains a carboxyl group. Therefore, X is desirably O.
- a preferred class of compounds are of the formula: wherein R, R 1 and R 4 are as defined above.
- a photo/moisture curable composition which includes a polymer according to structural formula II and an alkoxysilane according to structural formula IV wherein R is and R 5 , R 6 and R 7 are independently selected from hydrogen, halogen and organo radicals, and R 1 and R 4 are as described above.
- the structure of the silane capper used in the photo/moisture curing composition is an alkoxysilane of formula IV wherein R is structural formula V and R 5 and R 6 are H and R 7 is CH 3 .
- a particularly desired embodiment of the silane capper is that of structural formula VI below:
- the structure of the capper used in the curing composition of the invention is an alkoxysilane of structural formula IV wherein R is a methyl group and R 1 and R 4 are as described above.
- R is a methyl group and R 1 and R 4 are as described above.
- the desired structure is of structural formula VII below.
- silane cappers described above may be prepared by any desirable method known in the art.
- the synthesis of an acryloxy-functional alkoxysilane such as that of structural formulas VI may prepared by using the following reaction step:
- the proton in structural formula VII may be replaced with Na + or K + and reacted with structural formula IX.
- a base such as triethylamine under refluxing xylene or dimethylformamide
- a hydrogen chloride acceptor thereby removing the hydrogen chloride formed in the reaction.
- acrylate polymerization inhibitor such as hydroquinone (HQ) may also optionally be added to the mixture.
- structural formula I may be formed by reacting amino methyltrialkoxysilane with methacryl chloride.
- the reaction may be carried out at any suitable temperature; generally, temperatures on the order of from about 25 °C to about 150°C are usefully employed and preferably from about 100°C to 140°, most preferably at about 120°C.
- the time required to carry out the reaction may be readily determined for a given reaction system by simple analytical tests without undue experimentation, and the reaction time may be varied as necessary or desirable in a given application. By way of example, the reaction may be carried out in approximately 2-3 hours.
- the reaction mixture may optionally be subjected to vacuum stripping or other suitable treatment for the removal of residual acrylic acid from the reaction mixture to the extent desired.
- an alkoxysilane capper of the invention containing an acetoxy functional group may be prepared by reacting acetic acid with structure IX to yield a reaction product such as that of structure VII where R 1 is H.
- the silanol-terminated polymer of structural formula II can be virtually any useful silanol-terminated material.
- the silanol-terminated polymer as described above has the general formula wherein A represents a polymer or copolymer backbone.
- the backbone can be any number of combinations of polyurethane, silicone, polyamide, polyether and the like.
- A is an organic or a siloxane backbone. More desirably, A is a siloxane.
- silanol-terminated polymer having the formula:
- n can be, for example, an integer which, for example, can be from about 1 to about 1,200, desirably from about 10 to about 1,000.
- the viscosity of these materials is not critical and can easily be chosen to fit a particular product application, particularly because the hydrolyzable terminated end product of this reaction will have substantially the same viscosity as the silanol-terminated reactant. Viscosities of these silanol-terminated polymer backbone can range from about 1 cps to about 150,000 cps (Brookfield, 25°C).
- the silanol-terminated polymer backbone used in the present invention is from about 50 to about 150,000 cps.
- Useful silanol terminated polymers include those from about 50cps silanol-terminated polydimethylsiloxane, to about 150,000 cps silanol-terminated polydimethylsiloxane and combinations thereof.
- the invention also provides a curable composition including the reaction product of a silane capper as described above with the polymer of structural formula II also as described above.
- the reaction of structure I and II due to the carbon diradical linkage between the silicon in the capper and the-X-CO-R group enables a favorable hypervalent silicon transition state during the capping reaction resulting in fast nucleophilic substitution on silicon.
- this reaction product cures in less than about 20 minutes. More desirably the reaction product cures in less than about 15 minutes. Even more desirably, the reaction product cures between about 3 minutes and about 14 minutes. Yet, even more desirably, the reaction product cures in about 5 minutes.
- skin over time refers to the time it takes for a spatula to no longer pick up liquid upon contact with a reaction product.
- Desirable catalysts include organo-lithium reagents, which are represented by the formula LiR 12 wherein the organo group R 12 is selected from the group consisting of C 1-18 alkyl, C 1-18 aryl, C 1-18 alkylaryl, C 1-18 arylalkyl, C 2-18 alkenyl, C 2-18 alkynyl, amine-containing compounds, as well as organosilicon-containing compounds.
- R 12 can have from 1 to 18 carbon atoms in the chain (C 1-18 ).
- the organo-lithium catalyst is preferably an alkyl lithium such as methyl, n-butyl, sec-butyl, t-butyl, n-hexyl, 2-ethylhexyl butyl and n-octyl butyl lithium.
- a particularly desirable catalyst is N-butyllithium in hexane (such as at 1.6 Molar concentration).
- Other useful catalysts include phenyl lithium, vinyl lithium, lithium phenylacetylide, lithium (trimethylsilyl) acetylide, lithium silanolates and lithium siloxanolates.
- the organo group can also be an amine-containing compound, such as dimethylamide, diethylamide, diisopropylamide or dicyclohexylamide, or a silicon-containing compound.
- an amine-containing compound such as dimethylamide, diethylamide, diisopropylamide or dicyclohexylamide, or a silicon-containing compound.
- the organo-lithium reagents are used in catalytically effective amounts.
- the catalytically effective amount of an organo-lithium catalyst will vary with the specific catalyst and reactant materials, but about 1 to 1000 ppm based on the atomic weight of lithium are useful. A more preferred range is 5-250 ppm. Removal of the residual organo-lithium catalyst can be optionally accomplished through filtration.
- catalysts useful in, but less desirable, in preparing the reactive silicones include organometallic catalysts such as titanates and organo tin catalysts known in the art.
- the reactive silicone compositions of the invention may further include a curing system.
- a curing system includes but is not limited to catalysts or other reagents which act to accelerate or otherwise promote the curing of the composition of the invention.
- the catalysts which may be included in the curing system of the invention include, but are not limited to, tin IV salts of carboxylic acids, such as dibutyltin dilaurate, organotitanium compounds such as tetrabutyl titanate, and partially chelated derivatives of these salts with chelating agents such as acetoacetic acid esters and beta-diketones and amines.
- chelating agents such as acetoacetic acid esters and beta-diketones and amines.
- tetraisopropyltitanate, dibutyltin dilaurate and tetramethylguandine at levels of 0.05-0.5% are used.
- any known radical photoinitiators can be included in the compositions of the invention.
- Photoinitiators enhance the rapidity of the curing process when the photocurable compositions as a whole are exposed to electromagnetic radiation.
- suitable photointiators for use herein include, but are not limited to, photoinitiators available commercially from Ciba Specialty Chemicals, Tarrytown, New York under the "IRGACURE” and “DAROCUR” tradenames, specifically "IRGACURE” 184 (1-hydroxycyclohexyl phenyl ketone), 907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholino propan-1-one), 369 (2-benzyl-2-N,N-dimethylamino- 1 -(4-morpholinophenyl)- 1-butanone), 500 (the combination of 1-hydroxy cyclohexyl phenyl ketone and benzophenone), 651 (2,2-dimethoxy-2-phenyl
- photoinitiators useful herein include alkyl pyruvates, such as methyl, ethyl, propyl, and butyl pyruvates, and aryl pyruvates, such as phenyl, benzyl, and appropriately substituted derivatives thereof.
- Photoinitiators particularly well-suited for use herein include ultraviolet photoinitiators, such as 2,2-dimethoxy-2-phenyl acetophenone (e.g. , "IRGACURE” 651), and 2-hydroxy-2-methyl-1-phenyl-1-propane ( e.g. , "DAROCUR” 1173), diethoxyacetophenone, bis(2,4,6-trimethyl benzoyl) phenyl phosphine oxide (e.g.
- the amount of photoinitiator used in the composition will typically be in the range of between about 0.1 % and 5% of the composition. Depending on the characteristics of the particular photoinitiator, however, amounts outside of this range may be employed without departing from the invention so long as they perform the function of rapidly and efficiently initiating polymerization. In particular, higher percentages may be required if silicone bound photoinitiators are used with high equivalent weight per photoinitiating group.
- the inventive compositions may also contain other additives so long as they do not interfere with the curing mechanisms.
- the curable silicone compositions of the present invention can be mixed with or include other conventional additives such as viscosity modifiers such as trimethyl(silyl) terminated polydimethyl silicone, initiators, promoters, pigments, fillers, moisture scavengers and the like to form a one-part curable composition.
- Particularly useful fillers include fumed silica, silane treated, calcium carbonate, calcium carbonate (hydrophobic) and combinations thereof.
- Desirable pigments additives include carbon black.
- Moisture scavengers such as methyltrimethoxysilane and vinyltrimethyloxysilane are useful.
- adhesion promoters include, but are not limited to, such as glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, methacryloxypropyltrimethoxy-silane, triallyl-S-tria-zine-2,3,6(1H.3H.5H)-trione aminoethylaminopropyltrimethoxysilane and others known to those skilled in the art.
- Fillers such as silica, microballoon glass and the like are useful for their conventional purposes.
- the invention also provides a method of preparing a curable composition including the steps of reacting a silane capper according to structural formula I as described above with structural formula II.
- structural formula II may be devolitized under vacuum for an appropriate time period as is known in the art, generally 1-2 hours.
- the devolitization occurs at elevated temperatures, typically between 80°C to 150°C, more desirably between 100°C and 110°C.
- the silane capper is added to the silanol.
- a catalyst is used to increase the rate of capping.
- Desired catalysts include the organic lithium catalysts described above.
- N-butyllithium in hexane (1.6 M) is used. Endcapping under these conditions occurs immediately.
- silane capper of the invention and structural formula II may be utilized in any suitable proportions relative to one another consistent with the number of alcohol-reactive functional groups on structure II, it generally is preferred to utilize relative amounts of the inventive capper and structure II providing up to about 1.5 or more equivalents of silane for reaction with the silane of structure II, and desirably the equivalents ratio of silane to alcohol-reactive functionality is from about 1.0 to 1.2.
- the method also provides a curing system as described above.
- Desired catalyst for use in moisture curing include but are not limited to tetraisopropyltitanate, dibutyltin dilaurate and tetramethylguandine as well as photoinitiators including those described herein above.
- Fillers or reinforcing materials, adhesion promoters, anti-oxidants, flame retardants and pigments, etc may also optionally be provided in the method of the invention.
- a 500 ml three neck round bottom flask equipped with a mechanical stirrer and condenser were charged with 21.6 g sodium methacrylate, 40 ml dimethylformamide (DMF) and 0.04 grams of acrylate polymerization inhibitor, hydroquinone (HQ) and 34.20 g of chloromethyltrimethoxysilane.
- the mixture was heated under a closed system to 120°C for 2.5 hours. After cooling to room temperature, the mixture was vacuum filtered and the DMF distilled under vacuum at 40°C - 45°C. The crude reaction product was further vacuum fractionated to yield 24.54 g of the capper (56% yield).
- Capper VII was similarly prepared using sodium acetate and chloromethyltrimethoxysilane.
- Inventive polymer A was prepared by charging 1000g of a 750 cps of hydroxyl-terminated polydimethylsiloxane into a 2 liter three neck round bottom flask and devolitizing the fluid under vacuum at 105°C for one hour.
- the silanol was cooled to 75°C and 40.29 g of capper (structural formula VI) prepared according to Example 1 was added to the silanol along with 1 ml of N-butyllithium in hexane (1.6 Molar). Endcapping occurred immediately as evidenced by transformation of the clear silanol fluid into a cloudy mixture due to rapid boiling of the liberated methanol in silicone.
- the mixture was vacuum stripped with stirring at 75°C. 20 g of Polymer A was then used to assess skin over time.
- Polymer C was similarly prepared, but using capper VII instead.
- Example 3 Comparison of inventive polymer A with a Comparative polymer B.
- Comparative polymer B is of identical composition to inventive polymer A except that the comparative capped polymers contain a propyl rather a methyl linkage to the silicon.
- Methylacryloxypropyl dimethoxysiloxy-terminated PDMS was used as comparative polymer B.
- Polymer C was prepared similarly as in Example 2 using methacryloxy propyl trimethoxy silane instead of methacryloxy methyl trimethoxy silane.
- TIPT was prepared by mixing 0.1 g TIPT with 5 g of methyl-terminated poly(dimethylsiloxane) before its addition to the polymers.
- Table 1 Skin over time (SOT) Polymer A Comparative Polymer B 0.1 % TIPT 40 min. > 24 hours 0.2% TIPT 24 min. overnight 0.5% TIPT 12 min. 2.5-3 hours
- moisture curing using the reaction product of the composition of the invention results in a much faster cure in comparison to compositions prepared from a silane having a propenyl linkage rather than a methyl linkage linked to the silicon.
- Example 4 Skin over time of inventive polymer A in the presence of catalyst and photoinitiator.
- the skin over time was 3 minutes when 0.2% (tetramethylguanidine) TMG was added to the mixture.
- TMG 0.2%
- diethylacetophenone (DEAP) was also added, the moisture cure slowed to about 10 to 15 minutes.
- the formulation cured to silicone rubber when irradiated with a medium pressure mercury lamp with an intensity of 70 mW/cm 2 for 30 seconds.
- Example 5 Skin over time for inventive polymer C: comparison of catalysts and photoinitiator.
- composition C is an acetoxymethyltrimethoxysilane capped polydimethylsiloxane.
- the use of catalysts TIPT and TMG resulted in similar rates of skin over time.
- the addition of photoinitiator, diethylacetophenone (DEAP) increased the rate of skin over time when used with the catalyst TIPT.
- the effect on skin over time is not effected when DEAP is used with TMG.
- Examples 1-5 show that when the silane cappers used in the compositions have a methyl rather than a propyl linkage to the silane, faster curing in the presence of a moisture catalyst occurred, as measured by skin over time. Additionally, endcapping of the silanol occurred immediately upon addition of lithium catalyst.
- the examples also reveal that particular catalysts, such as TIPT, will increase the curing time when used with the photoinitiator, DEAP.
- the catalyst, TMG is not effected by DEAP and skin over time was 5 minutes.
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EP (1) | EP1578810B1 (ru) |
JP (1) | JP4754824B2 (ru) |
KR (1) | KR100967770B1 (ru) |
CN (1) | CN1705684B (ru) |
AT (1) | ATE358141T1 (ru) |
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CA (1) | CA2499186C (ru) |
DE (1) | DE60312891T2 (ru) |
MX (1) | MXPA05004222A (ru) |
PT (1) | PT1578810E (ru) |
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Families Citing this family (26)
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US20050234208A1 (en) * | 2004-04-14 | 2005-10-20 | Matthias Koch | Fast curing polydiorganosiloxanes |
FR2878855B1 (fr) * | 2004-12-07 | 2007-02-09 | Rhodia Chimie Sa | Procede de preparation de polyorganosiloxane a groupements fonctionnels en presence de silanolate de lithium |
WO2007061846A2 (en) * | 2005-11-22 | 2007-05-31 | Henkel Corporation | Moisture-curable silylated polymers for fast moisture curing compositions |
CN101360753A (zh) * | 2005-11-29 | 2009-02-04 | 汉高公司 | 辐射固化的硅酮组合物 |
US20070219285A1 (en) * | 2006-03-17 | 2007-09-20 | 3M Innovative Properties Company | Uv b-stageable, moisture curable composition useful for rapid electronic device assembly |
JP4302721B2 (ja) * | 2006-07-10 | 2009-07-29 | 信越化学工業株式会社 | 硬化性オルガノポリシロキサン組成物、それを含むフラットパネルディスプレイ用シール剤、及びフラットパネルディスプレイ素子 |
DE102007038661A1 (de) * | 2007-08-15 | 2009-02-19 | Henkel Ag & Co. Kgaa | Silanvernetzender Kleb- oder Dichtstoff mit N-Silylakylamiden und seine Verwendung |
EP2075281A1 (en) * | 2007-12-03 | 2009-07-01 | Borealis Technology OY | Polyolefin composition comprising crosslinkable polyolefin with silane groups, silanol condensation catalyst and silicon containing compound |
WO2009085183A2 (en) * | 2007-12-20 | 2009-07-09 | Henkel Corporation | Method of polymer bodying to obtain instant sealing of form-in-place engine gasketing sealants |
DE102009002231A1 (de) * | 2009-04-06 | 2010-10-07 | Wacker Chemie Ag | Bei Raumtemperatur selbsthaftende Pt-katalysierte additions-vernetzende Siliconzusammensetzungen |
DE102009045866A1 (de) * | 2009-10-20 | 2011-04-21 | Wacker Chemie Ag | Stabilisierte feuchtevernetzbare Polymere mit 2-phasiger Vernetzungskinetik |
DE102010010598A1 (de) * | 2010-03-08 | 2011-09-08 | Delo Industrie Klebstoffe Gmbh & Co. Kgaa | Dual härtende Masse und deren Verwendung |
CN102408569B (zh) * | 2010-09-21 | 2013-07-24 | 北京化工大学 | 一种可双固化聚硅氧烷丙烯酸酯树脂及其制备方法 |
US8901198B2 (en) | 2010-11-05 | 2014-12-02 | Ppg Industries Ohio, Inc. | UV-curable coating compositions, multi-component composite coatings, and related coated substrates |
CN102604224B (zh) * | 2012-03-16 | 2014-01-22 | 武汉富蒂亚新型材料有限公司 | 一种高熔体强度聚丙烯材料及其制备方法 |
CN102816551A (zh) * | 2012-05-23 | 2012-12-12 | 烟台信友电子有限公司 | 一种uv-湿气双固化液态光学透明胶及其制备方法 |
US8729179B1 (en) * | 2012-08-20 | 2014-05-20 | Henkel US IP LLC | Moisture curable polyacrylates |
GB201323041D0 (en) * | 2013-12-23 | 2014-02-12 | Dow Corning | Curable coating compositions containing an unsaturated alkoxysilane |
EP3092264B1 (en) * | 2014-01-08 | 2019-10-23 | Dow Silicones Corporation | Method for capping mq-type silicone resins |
CN103992650A (zh) * | 2014-04-11 | 2014-08-20 | 郝建强 | 紫外线/湿气双固化有机硅树脂组成物 |
EP3371232B1 (en) | 2015-11-03 | 2021-01-06 | LORD Corporation | Two-parts adhesive system |
US10035911B2 (en) | 2016-05-19 | 2018-07-31 | Momentive Performance Materials Inc. | Curable, dual cure, one part silicone composition |
CN108977163A (zh) * | 2017-06-05 | 2018-12-11 | 惠展电子材料(上海)有限公司 | 一种快干建筑密封胶组合物 |
KR102238704B1 (ko) | 2018-12-21 | 2021-04-08 | 주식회사 엘지화학 | 가교제 화합물, 이를 포함하는 감광성 조성물, 및 이를 이용한 감광 재료 |
CN111303776B (zh) * | 2020-03-09 | 2022-03-18 | 杭州电子科技大学 | 一种光-湿气固化组合物及其制备方法 |
CN113045697B (zh) * | 2021-02-04 | 2021-10-12 | 东莞市德聚胶接技术有限公司 | 一种改性丙烯酸酯低聚物及一种uv、湿气双重固化压敏胶 |
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US4675346A (en) * | 1983-06-20 | 1987-06-23 | Loctite Corporation | UV curable silicone rubber compositions |
US4528081A (en) * | 1983-10-03 | 1985-07-09 | Loctite Corporation | Dual curing silicone, method of preparing same and dielectric soft-gel compositions thereof |
US4699802A (en) * | 1983-10-03 | 1987-10-13 | Loctite Corporation | Dual curing coating method for substrates with shadow areas |
US5182315A (en) * | 1990-11-19 | 1993-01-26 | Loctite Corporation | Photocurable silicone gel composition, and method of making the same |
EP0512730B1 (en) * | 1991-05-06 | 1996-02-21 | Dow Corning S.A. | Manufacture of moisture curable organosiloxane compositions |
US5391677A (en) * | 1991-07-23 | 1995-02-21 | Shin-Etsu Chemical Co., Ltd. | Acrylic-functional organopolysiloxane and method for the preparation thereof |
US5340847A (en) * | 1991-10-23 | 1994-08-23 | Three Bond Co., Ltd. | Curable silicon composition |
JP3261592B2 (ja) * | 1992-04-20 | 2002-03-04 | 株式会社スリーボンド | 湿気硬化及び光硬化しうるシリコーン組成物 |
JP2639286B2 (ja) * | 1992-07-14 | 1997-08-06 | 信越化学工業株式会社 | 硬化性オルガノポリシロキサン組成物 |
EP0628605B1 (en) * | 1993-06-11 | 1999-08-04 | Three Bond Co., Ltd. | Moisture - or anaerobic-curable and photocurable silicone compositions |
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US5405888A (en) * | 1993-12-28 | 1995-04-11 | Three Bond Co, Ltd. | Curable silicone composition |
DE19725518A1 (de) * | 1997-06-17 | 1998-12-24 | Huels Silicone Gmbh | Polyorganosiloxane mit Dialkoxyorganosiloxy-Gruppen |
DE10219734A1 (de) * | 2002-05-02 | 2003-06-05 | Consortium Elektrochem Ind | Herstellung von (meth)acrylfunktionellen Siloxanen |
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- 2003-10-15 PT PT03777610T patent/PT1578810E/pt unknown
- 2003-10-15 US US10/524,542 patent/US7368519B2/en not_active Expired - Lifetime
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- 2003-10-15 KR KR1020057006939A patent/KR100967770B1/ko active IP Right Grant
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Also Published As
Publication number | Publication date |
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JP4754824B2 (ja) | 2011-08-24 |
US20050267276A1 (en) | 2005-12-01 |
AU2003287087A1 (en) | 2004-05-13 |
MXPA05004222A (es) | 2005-10-26 |
ATE358141T1 (de) | 2007-04-15 |
WO2004037868A1 (en) | 2004-05-06 |
CN1705684A (zh) | 2005-12-07 |
KR20050074968A (ko) | 2005-07-19 |
CA2499186A1 (en) | 2004-05-06 |
JP2006503960A (ja) | 2006-02-02 |
PT1578810E (pt) | 2007-06-18 |
DE60312891T2 (de) | 2007-12-13 |
EP1578810A1 (en) | 2005-09-28 |
US7368519B2 (en) | 2008-05-06 |
EP1578810A4 (en) | 2006-01-18 |
DE60312891D1 (de) | 2007-05-10 |
CA2499186C (en) | 2012-06-26 |
CN1705684B (zh) | 2013-03-27 |
KR100967770B1 (ko) | 2010-07-05 |
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